Herbicidal sulphonylated carboxamides

ABSTRACT

Herbicidal sulphonylated carboxamides of the formula 
     
         R.sup.1 --CO--NH--SO.sub.2 --(A).sub.n --R.sup.2           (I) 
    
     in which 
     n represents the numbers 0 or 1, 
     A represents oxygen, iminio (NH) or methylene (CH 2 ), 
     R 1  represents a five-membered heteroaryl radical which contains 1 or 2 nitrogen atoms and additionally one oxygen or sulphur atom in the ring and which is optionally substituted by halogen or by alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino or phenyl which are in each case optionally substituted, and 
     R 2  represents aryl or heteroaryl which are in each case optionally substituted, 
     or salts thereof, with the exclusion of the compound 2-dimethylamino-N-(4-methyl-phenylsulphonyl)-5-thiazole carboxamide.

This is a continuation-in-part of application Ser. No. 704,544, filedMay 23, 1991, now U.S. Pat. No. 5,205,853.

The invention relates to new sulphonylated carboxamides, processes fortheir preparation and their use as herbicides.

2-Dimethylamino-N-(4-methyl-phenylsulphonyl)-5-thiazole carboxamide isalready known from the literature as an example of sulphonylatedcarboxamides (compare J. Org. Chem. 46 (1981), 2790-2793). However,nothing has been published about the biological properties of thegeneral formula (I)

    R.sup.1 --CO--NH--SO.sub.2 --(A).sub.n --R.sup.2           (I)

in which

n represents the numbers 0 or 1,

A represents oxygen, imino (NH) or methylene (CH₂),

R¹ represents a five-membered heteroaryl radical which contains 1 or 2nitrogen atoms and additionally one oxygen or sulphur atom in the ringand which is optionally substituted by halogen or by alkyl, alkoxy,alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino orphenyl which are in each case optionally substituted, and

R² represents aryl or heteroaryl which are in each case optionallysubstituted,

and salts of compounds of the formula (I) have now been found, the known2-dimetylamino-N-(4-methyl-phenylsulphonyl)-5-thiazole carboxamide beingexcluded.

The new sulphonylated carboxamides of the formula (I) are obtained when

(a) carboxamides of the general formula (II)

    R.sup.1 --CO--NH.sub.2                                     (II)

in which

R¹ has the above mentioned meaning,

are reacted with sulphonylating agents of the general formula (III)

    X--SO.sub.2 --(A).sub.n --R.sup.2                          (III)

in which

n, A and R² have the abovementioned meanings and

X represents halogen,

if appropriate in the presence of an acid acceptor and if appropriate inthe presence of a diluent, or when

(b) carboxylic acids of the general formula (IV)

    R.sup.1 --COOH                                             (IV)

in which

R¹ has the abovementioned meaning, or reactive derivatives of carboxylicacids of the formula (IV)

are reacted with aminosulphonyl compounds of the general formula (V)

    H.sub.2 N--SO.sub.2 --(A).sub.n --R.sup.2                  (V)

in which

n, A and R² have the abovementioned meanings,

or with reactive derivatives of the compounds of the formula (V)

if appropriate in the presence of reaction auxiliaries and ifappropriate in the presence of diluents and, if appropriate, theproducts obtained by processes (a or (b) are converted into salts bycustomary methods.

The new sulphonylated carboxamides of the general formula (I) aredistinguished by strong herbicidal activity.

The invention preferably relates to sulphonylated carboxamides of theformula (I) in which

n represents the numbers 0 or 1,

A represents oxygen, imino (NH) or methylene (CH₂),

R¹ represents a five-membered heteroaryl radical from the seriescomprising oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyland thiadiazolyl, which is optionally monosubstituted orpolysubstituted, in particular monosubstituted or disubstituted, byidentical or different halogen or by optionally halogen-substituted C₁-C₆ -alkyl, phenyl, C₁ -C₆ -alkoxy, C₁ -C₆ -alkylthio, C₁ -C₆-alkylsulphinyl, C₁ -C₆ -alkylsulphonyl, C₁ -C₆ -alkylamino or di-(C₁-C₆ -alkyl)-amino, and

R² represents the radical ##STR1## in which R³ and R⁴ are identical ordifferent and represent hydrogen, fluorine, chlorine, bromine, iodine,cyano, nitro, carboxyl or C₁ -C₆ -alkyl which is optionally substitutedby fluorine, chlorine, bromine, cyano, carboxyl, C₁ -C₄ -alkoxycarbonyl,C₁ -C₄ -alkylamino-carbonyl, di-(C₁ -C₄ -alkyl)aminocarbonyl, hydroxyl,C₁ -C₄ -alkoxy, formyloxy, C₁ -C₄ -alkyl-carbonyloxy, C₁ -C₄-alkoxycarbonyloxy, C₁ -C₄ -alkylamino-carbonyloxy, C₁ -C₄ -alkylthio,C₁ -C₄ -alkylsulphinyl, C₁ -C₄ -alkylsulphonyl, di-(C₁ -C₄-alkyl)aminosulphonyl, C₃ -C₆ -cycloalkyl or phenyl, or R³ and R⁴furthermore independently of one another represent C₂ -C₆ -alkenyl whichis optionally substituted by fluorine, chlorine, bromine, cyano, C₁ -C₄-alkoxycarbonyl, carboxyl or phenyl, or R³ and R⁴ additionallyindependently of one another represent C₂ -C₆ -alkinyl which isoptionally substituted by fluorine, chlorine, bromine, cyano, C₁ -C₄-alkoxy-carbonyl, carboxyl or phenyl; C₁ -C₄ -alkoxy which is optionallysubstituted by fluorine, chlorine, bromine, cyano, carboxyl, C₁ -C₄-alkoxycarbonyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₁ -C₄-alkylsulphinyl or C₁ -C₄ -alkylsulphonyl; C₁ -C₄ -alkylthio which isoptionally substituted by fluorine, chlorine, bromine, cyano, carboxyl,C₁ -C₄ -alkoxycarbonyl, C₁ -C.sub. 4 -alkylthio, C₁ -C₄ -alkylsulphinylor C₁ -C₄ -alkylsulphonyl; C₃ -C₆ -alkenyloxy which is optionallysubstituted by fluorine, chlorine, bromine, cyano or C₁ -C₄-alkoxy-carbonyl, C₂ -C₆ -alkenylthio which is optionally substituted byfluorine, chlorine, bromine, cyano, nitro, C₁ -C₃ -alkylthio or C₁ -C₄-alkoxycarbonyl; C₃ -C₆ -alkynyloxy, C₃ -C₆ -alkylnylthio or the radical--S(O)_(p) --R⁵, or

R³ and R⁴ furthermore represent phenyl or phenoxy, C₁ -C₄-alkylcarbonylamino, C₁ -C₄ -alkoxycarbonylamino, C₁ -C₄-alkylamino-carbonylamino, di-(C₁ -C₄ -alkyl)-amino-carbonylamino, orthe radical --CO--R⁶, or R³ and R⁴ furthermore represent C₁ -C₄-alkylsulphonyloxy, di-(C₁ -C₄ -alkyl)-aminosulphonylamino or theradical --CH═N--R⁷, in which

p represents the numbers 1 or 2 and

R⁵ represents C₁ -C₄ -alkyl which is optionally substituted by fluorine,chlorine, bromine, cyano or C₁ -C₄ -alkoxycarbonyl or R⁵ represents C₁-C₄ -alkoxy, C₁ -C₄ -alkoxy-C₁ -C₄ -alkylamino or di(C₁ -C₄-alkyl)-amino,

R⁶ represents C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy which is optionallysubstituted by fluorine, chlorine, methoxy or ethoxy; C₃ -C₆-cycloalkoxy, C₃ -C₆ -alkenyloxy, C₁ -C₄ -alkylthio, amino, C₁ -C₄-alkylamino, C₁ -C₄ -alkoxyamino, C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl-amino ordi-(C₁ -C₄ -alkyl)amino which are optionally substituted by fluorineand/or chlorine and

R⁷ represents C₁ -C₆ -alkyl which is optionally substituted by fluorine,chlorine, cyano, carboxyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₁ -C₄-alkylsulphinyl or C₁ -C₄ -alkylsulphonyl, benzyl which is optionallysubstituted by fluorine or chlorine, C₃ -C₆ -alkenyl or C₃ -C₆ -alk nylwhich are optionally substituted by fluorine or chlorine, phenyl whichis optionally substituted by fluorine, chlorine, bromine, C₁ -C₄ -alkyl,C₁ -C₄ -alkoxy, trifluoromethyl, trifluoromethoxy ortrifluoromethylthio, C₁ -C₆ -alkoxy, C₃ -C₆ -alkenyloxy, C₃ -C₆-alkynyloxy or benzyloxy which are optionally substituted by fluorineand/or chlorine, or R⁷ furthermore represents amino, C₃ -C₄ -alkylamino,di-(C₁ -C₄ -alkyl)-amino, phenylamino, C₁ -C₄ -alkyl-carbonylamino, C₁-C₄ -alkoxy-carbonylamino, C₁ -C₄ -alkylsulphonylamino or phenylsulphonylamino which is optionally substituted by fluorine, chlorine,bromine or methyl,

R⁸ and R⁹ are identical or different and represent hydrogen, fluorine,chlorine, bromine, nitro, cyano, C₁ -C₄ -alkyl which is optionallysubstituted by fluorine and/or chlorine; or C₁ -C₄ -alkoxy which isoptionally substituted by fluorine and/or chlorine;

R¹⁰ and R¹¹ are identical or different and represent hydrogen, fluorine,chlorine, bromine, nitro, cyano, or C₁ -C₄ -alkyl which is optionallysubstituted by fluorine and/or chlorine; C₂ -C₄ -alkenyl which isoptionally substituted by fluorine and/or chlorine, C₁ -C₄ -alkoxy whichis optionally substituted by fluorine and/or chlorine, C₁ -C₄-alkylthio, C₁ -C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl which areoptionally substituted by fluorine and/or chlorine; and di-(C₁ -C₄-alkyl)-aminosulphonyl, C₁ -C₄ -alkoxy-carbonyl, dimethylaminocarbonylor dioxolanyl;

R¹² and R¹³ are identical or different and represent hydrogen, fluorine,chlorine; bromine or C₁ -C₄ -alkyl which is optionally substituted byfluorine and/or chlorine; C₁ -C₄ -alkoxy which is optionally substitutedby fluorine and/or chlorine; C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinylor C₁ -C₄ -alkylsulphonyl which are optionally substituted by fluorineand/or chlorine; or di-(C₁ -C₄ -alkyl)aminosulphonyl;

R¹⁴ and R¹⁵ are identical or different and represent hydrogen, fluorine,chlorine, bromine, cyano, nitro or C₁ -C₄ -alkyl which is optionallysubstituted by fluorine, chlorine, C₁ -C₄ -alkoxy and/or C₁ -C₄-halogenoalkoxy; C₁ -C₄ -alkoxy which is optionally substituted byfluorine and/or chlorine; C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl orC₁ -C₄ -alkylsulphonyl which are optionally substituted by fluorineand/or chlorine, di-(C₁ -C₄ -alkyl)-amino-sulphonyl or C₁ -C₄-alkoxycarbonyl, and

A¹ represents oxygen, sulphur or the group N--Z¹, in which

Z¹ represents hydrogen or C₁ -C₄ -alkyl which is optionally substitutedby fluorine, chlorine, bromine or cyano; C₃ -C₆ -cycloalkyl, benzyl orphenyl, phenyl optionally being substituted by fluorine, chlorine,bromine or nitro; C₁ -C₄ -alkylcarbonyl, C₁ -C₄ -alkoxy-carbonyl ordi-(C₁ -C₄ -alkyl)aminocarbonyl,

R¹⁶ and R¹⁷ are identical or different and represent hydrogen, C₁ -C₄-alkyl, halogen, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkoxy or C₁ -C₄-halogenoalkoxy,

Y¹ represents sulphur or the group N--R¹⁸, in which R¹⁸ representshydrogen or C₁ -C₄ -alkyl,

R¹⁹ represents hydrogen, C₁ -C₄ -alkyl, phenyl or (iso)quinolinyl,

R²⁰ represents hydrogen, halogen, cyano, nitro or C₁ -C₄ -alkyl which isoptionally substituted by fluorine and/or chlorine; C₁ -C₄ -alkoxy whichis optionally substituted by fluorine and/or chlorine; dioxolanyl or C₁-C₄ -alkoxy-carbonyl,

R²¹ represents hydrogen, halogen or C₁ -C₄ -alkyl,

R²² represents hydrogen, halogen, C₁ -C₄ -alkyl or C₁ -C₄-alkoxy-carbonyl,

R²³ represents C₁ -C₄ -alkyl,

R²⁴ represents C₁ -C₄ -alkyl and

R²⁵ represents hydrogen or methyl,

excluding the compound2-(dimethylamino)-N-[(4-methylphenyl)sulphonyl]-5-thiazole carboxamide.

The invention relates in particular to compounds of the formula (I) inwhich

n represents the numbers 0 or 1,

A represents oxygen, imino (NH) or methylene (CH₂),

R¹ represents a five-membered heteroaryl radical from the seriescomprising oxazolyl, isoxazolyl, thiazolyl, 1,2,4-oxadiazolyl,1,3,4-oxadiazolyl, 1,2,4-thiadiazolyl and 1,3,4-thiadiazolyl, which isoptionally substituted by fluorine, chlorine, bromine, methyl, ethyl,propyl, isopropy, butyl, isobutyl, sec-butyl, tert-butyl, fluoromethyl,chloromethyl, difluoromethyl, dichloromethyl, trifluoromethyl,trichloromethyl, chlorofluoromethyl, chlorodifluoromethyl,fluorodichloromethyl, phenyl, methoxy, ethoxy, propoxy, isopropyloxy,difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, methylthio,ethylthio, propylthio, isopropylthio, difluoromethylthio,trifluoromethylthio, chlorodifluoromethylthio, methylsulphinyl,ethylsulphinyl, propylsulphinyl, methylsulphonyl, ethylsulphonyl,propysulphonyl, methylamino, ethylamino, propylamino, isopropylaminoand/or dimethylamino, and

R² represents the radical ##STR2## R³ represents hydrogen, fluorine,chlorine, bromine, cyano, nitro, carboxyl, methyl, trifluoromethyl,methoxy, ethoxy, 2-chloroethoxy, difluoromethoxy, trifluoromethoxy, C₁-C₃ -alkylthio, C₁ -C₃ -alkyl-sulphinyl, C₁ -C₃ -alkylsulphonyl,dimethylaminosulphonyl, diethylaminosulphonyl,N-methoxy-N-methylaminosulphonyl, phenyl, phenoxy or C₁ -C₃-alkoxycarbonyl and

R⁴ represents hydrogen, fluorine, chlorine, bromine, methyl,trifluoromethyl or methoxy;

R¹⁰ represents dimethylaminocarbonyl or C₁ -C₄ -alkylsulphonyl,

R¹¹ represents hydrogen, fluorine or chlorine and

R represents methyl or ethyl,

excluding the compound2-(dimethylamino)-N-[(4-methylphenyl)-sulphonyl]-5-thiazole carboxamide.

n in particular represents the number 0. If n represents the number 1, Ain particular represents CH₂.

R² in particular represents ##STR3## where R³ and R⁴ are preferably inthe orthoposition. R⁴ in particular represents hydrogen.

The invention further preferably relates to salts of compounds of theformula (I) with bases, such as, for example, the hydroxide, hydride,amide or carbonate of sodium, potassium or calcium, C₁ -C₄ -alkoxides ofsodium or potassium, ammonia, C₁ -C₄ -alkylamines, di-(C₁ -C₄-alkyl)amines or tri-(C₁ -C₄ -alkyl)-amines.

Examples of the compounds of the formula (I) according to the inventionare shown in Table 1 below.

    R.sup.1 --CO--NH--SO.sub.2 --(A).sub.n --R.sup.2           (I)

                  TABLE 1    ______________________________________    Examples of the compounds of the formula (I)    R.sup.1        A      n     R.sup.2    ______________________________________     ##STR4##      --     0                                 ##STR5##     ##STR6##      --     0                                 ##STR7##     ##STR8##      --     0                                 ##STR9##     ##STR10##     --     0                                 ##STR11##     ##STR12##     --     0                                 ##STR13##     ##STR14##     --     0                                 ##STR15##     ##STR16##     --     0                                 ##STR17##     ##STR18##     --     0                                 ##STR19##     ##STR20##     --     0                                 ##STR21##     ##STR22##     --     0                                 ##STR23##     ##STR24##     --     0                                 ##STR25##     ##STR26##     --     0                                 ##STR27##     ##STR28##     --     0                                 ##STR29##     ##STR30##     --     0                                 ##STR31##     ##STR32##     --     0                                 ##STR33##     ##STR34##     --     0                                 ##STR35##     ##STR36##     --     0                                 ##STR37##     ##STR38##     --     0                                 ##STR39##     ##STR40##     --     0                                 ##STR41##     ##STR42##     --     0                                 ##STR43##     ##STR44##     --     0                                 ##STR45##     ##STR46##     --     0                                 ##STR47##     ##STR48##     --     0                                 ##STR49##     ##STR50##     --     0                                 ##STR51##     ##STR52##     --     0                                 ##STR53##     ##STR54##     --     0                                 ##STR55##     ##STR56##     --     0                                 ##STR57##     ##STR58##     --     0                                 ##STR59##     ##STR60##     --     0                                 ##STR61##     ##STR62##     --     0                                 ##STR63##     ##STR64##     --     0                                 ##STR65##     ##STR66##     --     0                                 ##STR67##     ##STR68##     --     0                                 ##STR69##     ##STR70##     --     0                                 ##STR71##     ##STR72##     --     0                                 ##STR73##     ##STR74##     --     0                                 ##STR75##     ##STR76##     CH.sub.2                          1                                 ##STR77##    ______________________________________

If, for example, 2-trifluoromethyl-oxazole-4-carboxamide and2-cyano-phenylmethanesulphonyl chloride are used as starting materialsin process (a) according to the invention, the course of the reactioncan be outlines by the following equation: ##STR78##

If, for example, methyl 5-methyl-isoxazole-3-carboxylate and2,6-difluoro-benzene-sulphonamide are used as starting materials inprocess (b) according to the invention, the course of the reaction canbe outlined by the following equation: ##STR79##

Formula (II) provides a general definition of the carboxamides to beused as starting materials in process (a) according to the invention forthe preparation of compounds of the formula (I).

In formula (II), R¹ preferably or in particular has that meaning whichhas already been mentioned above as preferred or as particularlypreferred for R¹ in connection with the description of the compounds ofthe formula (I) according to the invention.

Examples of the starting materials of the formula (II) which may bementioned are: 5-methyl-, 5-ethyl-, 5-propyl-, 5-isopropyl-, 5-butyl-,5-isobutyl-, 5-sec-butyl- and 5-tert-butyl-isoxazole-3-carboxamide,2-methyl-, 2-ethyl-, 2-propyl-, 2-isopropyl-, 2-butyl-, 2-isobutyl-,2-sec-butyl- and 2-tertbutyl-oxazole-4-carboxamide, 5-methyl-, 5-ethyl-,5-propyl-, 5-isopropyl-, 5-butyl-, 5-isobutyl-, 5-secbutyl- and5-tert-butyl-1,2,4-oxadiazole-3-carboxamide, 2-chloro-, 2-methyl-,2-ethyl-, 2-propyl-, 2-isopropyl-, 2-butyl-, 2-isobutyl-, 2-sec-butyl-,2-tert-butyl-, 2-trifluoromethyl-, 2-methoxy-, 2-ethoxy-, 2-propoxy- and2-isopropoxy-thiazole-5-carboxamide,2,4-dichloro-thiazole-5-carboxamide,2-methyl-4-chloro-thiazole-5-carboxamide,2-methoxy-4-chloro-thiazole-5-carboxamide, 4-methyl-, 4-ethyl-,4-propyl-, 4-isopropyl-, 4-butyl-, 4-isobutyl-, 4-sec-butyl- and4-tert-butyl-thiazole-2-carboxamide, 5-methyl-, 5-ethyl-, 5-propyl-, 5-isopropyl-5-butyl-, 5-isobutyl-, 5-sec-butyl- and5-tert-butylthiazole-2-carboxamide.

The carboxamides of the formula (II) are known and/or can be prepared bymethods known per se (compare RO-P 67,530 cited in Chem. Abstracts 95,7258k; Helv. Chim. Acta 27 (1944), 1437-1438; Chem. Ber. 73 (1940),1240-1252; J. Prakt. Chem. 314 (1972), 447-454).

Formula (III) provides a general definition of the sulphonylating agentsfurther required as starting materials in process (a) according to theinvention.

In formula (III), n, A and R² preferably or in particular have thosemeanings which have already been mentioned above as preferred or asparticularly preferred for n, A and R² in connection with thedescription of the compounds of the formula (I) according to theinvention and

X preferably represents fluorine, chlorine or bromine, in particularchlorine.

Examples of the starting materials of the formula (III) which may bementioned are: benzenesulphonyl chloride, 2-chloro-, 3-chloro-,4-chloro-, 2,5-dichloro-, 2-fluoro-, 4-fluoro-, 2-bromo-, 4-bromo-,2-cyano-, 2-nitro-, 4-nitro-, 2-methyl-, 4-methyl-, 2-chloromethyl-,2-trifluoromethyl-, 2-methoxy-4-methoxy-, 2-methylthio,2-trifluoromethylthio-, 2-difluoromethylthio-,2-cyclopropyloxycarbonyl-, 2-phenoxy-, 2-difluoromethoxy-,2-trifluoromethoxy-, 2-(2-chloroethoxy)-, 2-methylthiomethyl-,2-dimethylaminosulphonyl-, 2-phenyl-, 2-methoxycarbonyl-,2-ethoxycarbonyl-, 2-dimethylaminocarbonyl and2-diethylaminocarbonyl-benzenesulphonyl chloride and also(2-chlorophenyl)-, (2-cyano-phenyl)-, (2-methoxycarbonyl-phenyl)- and(2-trifluoromethoxy-phenyl)-methanesulphonyl chloride,2-chloro-6-methyl-benzenesulphonyl chloride and2,6-dichloro-benzenesulphonyl chloride.

The sulphonylating agents of the formula (III) are known and/or can beprepared by processes which are known per se ()compare J. Org. Chem. 33(1968), 2104; J. Org. Chem. 25 (1960), 1824; DE-AS (German PublishedSpecification) 2,308,262; EP-OS (European Published Specification)23,140, 23,141, 23,422, 35,893, 48,143, 51,466, 64,322, 70,041, 44,808and 44,809; U.S. Pat. Nos. 2,929,820, 4,282,242; 4,348,220 and 4,372,778and also Angew. Chem. 93 (1981), 151).

Process (a) according to the invention for the preparation of the newcompounds of the formula (I) is preferably carried out using diluents.Suitable diluents in this case are virtually all the inert organicsolvents. These preferably include aliphatic and aromatic, optionallyhalogenated hydrocarbons such as pentane, hexane, heptane, cyclhexane,petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylenechloride, ethylene chloride, chloroform, carbon tetrachloride,chlorobenzene and o-dichlorobenzene, ethers such as diethyl ether anddibutyl ether, glycol dimethyl ether and diglycol dimethyl ether,tetrahydrofuran and dioxane, ketones such as acetone, methyl ethylketone, methyl isopropyl ketone and methyl isobutyl ketone, esters suchas methyl acetate and ethyl acetate, nitriles such as, for example,acetonitrile and propionitrile, amides such as, for example,dimethylformamide, dimethylacetamide and N-methyl-pyrrolidone and alsodimethyl sulphoxide, tetramethylene sulphone and hexamethylphosphorictriamide and pyridine.

Acid acceptors which can be employed in process (a) according to theinvention are all acid-binding agents which can customarily be used forreactions of this type. Those which are preferable are alkali metalhydroxides such as, for example, sodium hydroxide and potassiumhydroxide, alkaline earth metal hydroxides such as, for example, sodiumhydride and potassium hydride, alkaline earth metal hydrides such as,for example, calcium hydride, alkali metal carbonates and alkoxides suchas sodium carbonate and potassium carbonate, sodium tert.-butoxide andpotassium tert.-butoxide, and in addition aliphatic, aromatic orheterocyclic amines, for example triethylamine, trimethylamine,dimethylaniline, dimethylbenzylamine, pyridine, picoline,1,5-diazabicyclo-[4.3.0]-non5-ene (DBN),1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) and1,4-diazabicyclo-[2.2.2]-octane (DABCO).

To carry out process (a) according to the invention, the startingmaterials required in each case are in general employed in approximatelyequimolar amounts. However, it is also possible to use one of the twocomponents employed in each case in a relatively large excess. Thereaction are in general carried out in a suitable diluent in thepresence of an acid acceptor, and the reaction mixture is stirred forseveral hours at the temperature required in each case. Working-up is ineach case carried out in process (a) according to the invention bycustomary methods (compare the preparation examples).

Formula (IV) provides a general definition of the carboxylic acidsrequired as starting materials in process (b) according to theinvention.

In formula (IV), R¹ preferably or in particular has that meaning whichhas already been indicated as preferred or as particularly preferred forR¹ in connection with the description of the compounds of the formula(I) according to the invention.

Examples of the starting materials of the formula (IV) which may bementioned are: 5-methyl-, 5-ethyl-, 5-propyl-, 5-isopropyl-, 5-butyl-,5-isobutyl-, 5-sec-butyl- and 5-tert-butyl-isoxazole-3-carboxylic acid,2-methyl-, 2-ethyl-, 2-propyl-, 2-isopropyl-, 2-butyl, 2-isobutyl-,2-sec-butyl- and 2-tert-butyl-oxazole-4-carboxylic acid, 5-methyl-,5-ethyl-, 5-propyl-, 5-isopropyl-, 5-butyl-, 5-isobutyl-, 5-sec-butyl-and 5-tert-butyl-1,2,4-oxadiazole-3-carboxylic acid, 2-chloro,2-methyl-, 2-ethyl-, 2-propyl-, 2-isopropyl-, 2-butyl-, 2-isobutyl-,2-sec-butyl, 2-tertbutyl-, 2-trifluoromethyl-, 2-methoxy-, 2-ethoxy-,2-propoxy- and 2-isopropyl-thiazole-5-carboxylic acid,2,4-dichloro-thiazole-5-carboxylic acid,2-methyl-4-chloro-thiazole-5-carboxylic acid,2-methoxy-4-chloro-thiazole-5-carboxylic acid, 4-methyl-, 4-ethyl-,4-propyl, 4-isopropyl-, 4-butyl-, 4-isobutyl-, 4-sec-butyl- and4-tert-butyl-thiazole-2-carboxylic acid, 5-methyl-, 5-ethyl-, 5-propyl-,5-isopropyl-, 5-butyl-, 5-isobutyl-, 5-sec-butyl- and5-tert-butyl-thiazole-2-carboxylic acid.

The carboxylic acids of the formula (IV) are known and/or can beprepared by known processes (compare GB-P 1,245,517; DE-OS (GermanPublished Specification) 2,940,189; DE-OS (German PublishedSpecification) 3,013,908; Helv. Chim. Acta 27 (1944), 1437-1438; Chem.Ber. 73 (1940), 1240-1252; J. Chem. Soc. 1946, 87-91; loc. cit. 1947,96-102; Helv. Chim. Acta 29 (1946), 1957-1959; J. Prakt. Chem. 314(1972), 447-454; Chem. Ber. 94 (1961), 757-761).

Instead of the carboxylic acids of the formula (IV), the carbonylchlorides derived therefrom or alkyl esters derived therefrom(preferably methyl esters or ethyl esters), aralkyl esters (preferablybenzyl esters) or aryl esters (preferably phenyl esters, optionallysubstituted in the phenyl group by cyano, nitro, chlorine, fluorine,bromine and/or methyl) may be employed as starting materials ("reactivederivatives") in process (b) according to the invention.

The carbonyl chlorides are obtained from the corresponding carboxylicacids by customary methods, for example by reaction with customary"chlorinating agents" such as, for example, phosgene, oxalyl chloride orthionyl chloride, if appropriate in the presence of reactionauxiliaries, such as, for example, pyridine, and if appropriate in thepresence of diluents, such as, for example, chloroform ortetrachloromethane, at temperatures between 0° C. and 100° C.

The corresponding esters of the formula (IV) can be obtained from theappropriate carbonyl chlorides and suitable alcohols or phenols bycustomary methods, in general by reaction in the presence of an acidacceptor, such as, for example, triethylamine or pyridine, and in thepresence of a diluent, such as, for example, acetonitrile, attemperatures between 0° C. and 100° C.

However, the esters mentioned can also be obtained directly from thecarboxylic acids of the formula (IV) in the presence of condensationauxiliaries, such as, for example, dicyclohexylcarbodiimide, ifappropriate in the presence of reaction auxiliaries, such as, forexample, 4-dimethylamino-pyridine, and if appropriate in the presence ofdiluents, such as, for example, methylene chloride or chloroform, attemperatures between 0° C. and 100° C.

Formula (V) provides a general definition of the aminosulphonylcompounds further required as starting materials in process (b)according to the invention.

In formula (V), n, A and R² preferably or in particular have thosemeanings which have preferred for n, A and R² in connection with thedescription of the compounds of the formula (I) according to theinvention.

Examples of the starting materials of the formula (V) which may bementioned are: benzenesulphonamide, 2-chloro-, 3-chloro-, 4-chloro-,2,5-dichloro-, 2-fluoro-, 4-fluoro-, 2-bromo-, 4-bromo-, 2-cyano-,2-nitro-, 4-nitro-, 2-methyl-, 4-methyl-, 2-chloromethyl-,2-trifluoromethyl-, 2-methoxy-, 4-methoxy-, 2-methylthio-,2-trifluoromethylthio-, 2-difluoromethylthio-,2-cyclopropyloxycarbonyl-, 2-phenoxy-, 2-difluoromethoxy-,2-trifluoromethoxy-, 2-(2-chloroethoxy), 2-methylthiomethyl-,2-dimethylaminosulphonyl-, 2-phenyl-, 2-methoxycarbonyl-,2-ethoxycarbonyl-, 2-dimethylaminocarbonyl- and2-diethylaminocarbonylbenzenesulphonamide and also (2-chloro-phenyl)-,(2-cyano-phenyl)-, (2-methoxycarbonyl-phenyl)- and(2-trifluoromethoxy-phenyl)-methanesulphonamide,2-chloro-6-methyl-benzenesulphonyl chloride and2,6-dichlorobenzenesulphonamide.

The aminosulphonyl compounds of the formula (V) are known and/or can beprepared by process which are known per se (compare J. Org. Chem. 33(1968), 2104; J. Org. Chem. 25 (1960), 1824; DE-AS (German PublishedSpecification) 2,308,262; EP-A 23,140, 23,141, 23,422, 35,893, 48,143,51,466, 64,322, 70,041, 44,808 and 44,809; U.S. Pat. Nos. 2,929,820,4,282,242; 4,348,220 and 4,372,778 and also Angew. Chem. 93 (1981),151).

Instead of the aminosulphonyl compounds of the formula (V), thesulphonyl isocyanates derived therefrom ("reactive derivatives") may beemployed as starting materials in process (b) according to the ininvention. These compounds are known and/or can be prepared by methodswhich are known per se (compare J. Org. Chem. 31 (1966), 2658-2661; EP-A7687; EP-A 46,626; EP-A 21,641; EP-A 23,140; EP-A 23,141; EP-A 70,041;EP-A 23,422, EP-A 64,322; EP-A 34,431; EP-A 35,893; EP-A 51,466, EP-A44,808; EP-A 173,312, DE-OS (German Published Specification) 3,132,944;EP-A 87,780; EP-A 271,780).

Process (b) according to the invention for the preparation of the newcompounds of the formula (I) is preferably carried out using diluents.Possible diluents in this case are preferably the same diluents whichare indicated above for process (a) according to the invention.

Process (b) according to the invention is optionally carried out in thepresence of a reaction auxiliary. Suitable reaction auxiliaries in thiscase are compounds with which carboxylic acids are converted intoreactive intermediates which are then reacted in situ with nucleophiliccompounds, such as, for example, the sulphonamides of the formula (V) togive corresponding carboxylic acid derivatives. Examples of reactionauxiliaries of this type which may be mentioned are carbonyldiimidazoleand 2-chloro-1-methyl-pyridinium iodide.

For the reaction of the carbonyl chlorides and esters according toformula (IV) with aminosulphonyl compounds of the formula (V), acidacceptors such as have been indicated above for process (a) according tothe invention are also suitable as reaction auxiliaries.

The reaction temperatures in process (b) according to the invention canbe varied within a substantial range. In general, the reaction iscarried out at temperatures between 0° C. and 150° C., preferably attemperatures between 10° C. and 100° C.

Process (b) according to the invention is in general carried out undernormal pressure. However, it is also possible to work at elevated orreduced pressure.

To carry out process (b) according to the invention, the startingmaterials required in each case are in general employed in approximatelyequimolar amounts. However it is also possible to use one of the twocomponents employed in each case in a relatively large excess. Thereactions are in general carried out in the presence of a suitablediluent and if appropriate in the presence of a reaction auxiliary, andthe reaction mixture is stirred for several hours at the temperaturerequired in each case. Working-up is carried out by customary methods.

Salts may optionally be prepared from the compounds of the generalformula (I) according to the invention. Such salts are obtained in asimple manner by customary salt formation methods, for example bydissolving or dispersing a compound of the formula (I) in a suitablesolvent, such as, for example, water, methanol, ethanol, methylenechloride or acetone, and adding a suitable acid or base. The salts canthen be isolated--if appropriate after stirring for a relatively longtime --by concentrating or filtering off with suction.

The active compounds according to the invention can be used asdefoliants, desiccants, agents for destroying broad-leaved plants and,especially, as weedkillers. By weeks, int he broadest sense, there areto be understood all plants which grow in locations where they areundesired. Whether the substances according to the invention act astotal or selective herbicides depends essentially on the amount used.

The active compounds according to the invention can be used, forexample, in connection with the following plants:

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria,Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio,Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum,Sesbania, Ambrosia, Cirsium, Carduus, Conchus, Solanum, Rorippa, Rotala,Lindernia, Lamiu, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis,Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus,Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana,Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.

Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum,Digitaria, Phleum, Poa, Festuca, Elusine, Brachiaria, Lolium, Bromus,Avena, Cyperus, Sorghum, Agropyron, Gynodon, Monochoria, Fimbristylis,Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea,Dactyloctenium, Agrostis, Alopecurus and Apera.

Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum,Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus andAllium.

However, the use of the active compounds according to the invention isin no way restricted to these genera, but also extends in the samemanner to other plants.

The compounds are suitable, depending on the concentration, for thetotal combating of weeds, for example on industrial terrain and railtracks, and on paths and squares with or without tree plantings.Equally, the compounds can be employed for combating weeds in perennialcultures, for example aforestations, decorative tree plantings,orchards, vineyards, citrus groves, nut orchards, banana plantations,coffee plantations, tea plantations, rubber plantation, oil palmplantations, cocoa plantations, soft fruit plantings and hopfields, onlawns, turf and pastureland and for the selective combating of weeds inannual cultures.

The compounds of the formula (I) are in particular suitable for theselective combating of dicotyledon weeds in monocotyledon cultures, suchas, for example, in corn and wheat, both in the pre-emergence and in thepost-emergence process.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusting agents, pastes, soluble powders, granules, suspension-emulsionconcentrates, natural and synthetic materials impregnated with activecompound, and very fine capsules in polymeric substances.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is liquid solvents and/orsolid carriers, optionally with the use of surface-active agents, thatis emulsifying agents and/or dispersing agents and/or foam-formingagents.

In the case of the use of water as an extender, organic solvents can,for example, also be used as auxiliary solvents. As liquid solvents,there are suitable in the main: aromatics, such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics and chlorinated aliphatichydrocarbons, such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, forexample petroleum fractions, mineral and vegetable oils, alcohols, suchas butanol and glycol as well as their ethers and esters, ketones, suchas acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethyl sulphoxide, as well as water.

As solid carriers there are suitable: for example ammonium salts andground natural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly disperse silica, alumina and silicates, assolid carriers for granules there are suitable: for example crushed andfractionated natural minerals such as calcite, marble, pumice, sepioliteand dolomite, as well as synthetic granules of inorganic and organicmeals, and granules or organic material such as sawdust, coconut shells,corn cobs and tobacco stalks; as emulsifying and/or foam-forming agentsthere are suitable: for example non-ionic and anionic emulsifiers, suchas polyoxyethylene fatty acid esters, polyoxyethylene fatty alcoholethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates as well as albumin hydrolysis products; asdispersing agents there are suitable: for example ligninsulphite wasteliquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latexes, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Further additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 percent by weightof active compound, preferably between 0.5 and 90%.

For controlling weeds, the active compounds according to the invention,as such or in the form of their formulations, can also be used asmixtures with known herbicides, finished formulations or tank mixesbeing possible.

Suitable herbicides for the mixtures are known herbicides, such as, forexample,1-amino-6-ethylthio-3-(2,2-dimethylpropyl)-1,3,5-triazine-2,4(1H,3H)-dione(AMETHYDIONE) OR N-(2-benzothiazolyl)-N,N'-dimethylurea(METABENZTHIAZURON) for combating weeds in cereals;4-amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one (METAMITRON) forcombating weeds in sugar beets and4-amino-6-(1,1-dimethylethyl)-3-methylthio-1,2,4-triazin-5(4H)-one(METRIBUZIN) for combating weeds in soy beans; in addition also2,4-dichlorophebnoxyacetic acid (2,4-D); 4-(2,4-dichlorophenoxy)-butyricacid (2,4-DB); 2,4-dichlorophenoxypropionic acid (2,4-DP);2-chloro-2',6'-diethyl-N-methoxymethyl-acetanilide (ALACHLOR);2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine (ATRAZINE);3-isopropyl-2,1,3-benzothiadiazin-4-one-2,2-dioxide (BENTAZONE); METHYL5-(2,4-dichlorophenoxy)-2-nitrobenzoate (BIFENOX);3,5-dibromo-4-hydroxy-benzonitrile (BROMOXYNIL);2-chloro-N-{[(4-methoxy-6-methyl-1,3,5-traizin-2-yl)-amino]-carbonyl}benzenesulphonamide(CHLORSULFURON); N,N-dimethyl-N'-(3-chloro-4-methylphenyl)-urea(CHLOROTOLURON);2-chloro-4-ethylamino-6-(3-cyanopropylamino);-1,3,5-triazine(CYANAZINE); 2-[4-(2,4-dichlorophenoxy)-phenoxy]-propionic acid, itsmethyl ester or its ethyl ester (DICLOFOP);4-amino-6-t-butyl-3-ethylthio-1,2,4-triazin-5(4H)-one (ETHIOZIN);2-{4-[(6-chloro-2-benzoxazolyl)-oxy]-phenoxy}-propanoic acid, its methylester or its ethyl ester (FENOXAPROP);[(4-amino-3,5-dichloro-6-fluoro-2-pyridinyl)-oxy]-acetic acid or its1-methylheptyl ester (FLUROXYPYR); N-phosphonomethylglycine(GLYPHOSATE);methyl-2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-4(5)-methylbenzoate (IMAZAMETHABENZ); 3,5-diiodo-4-hydroxybenzonitrile(IOXYNIL); N,N-dimethyl-N'-(4-isopropylphenyl)urea (ISOPROTURON);(2-methyl-4-chlorophenoxy)-acetic acid (MCPA);(4-chloro-2-methylphenoxy)-propionic acid (MCPP);2-ethyl-6-methyl-N-(1-methyl-2-methoxyethyl)chloroacetanilide(METOLACHLOR);2-{[[((4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino)-carbonyl]-amino-sulphonyl}-benzoicacid or its methyl ester (METSULFURON);N-(1-ethylpropyl)-3,4-dimethyl-2,6-dinitroaniline (PENDIMETHALIN);O-(6-chloro-3-phenyl-pyridazin-4-yl) S-octyl thiocarbonate (PYRIDATE);4-ethylamino-2-t-butylamino-6-methylthio-s-triazine (TERBUTRYNE); methyl3-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]carbonyl]-amino]-sulphonyl]-thiophene-2-carboxylate(THIAMETURON); and S-(2,3,3-trichloroallyl) N,N-diisopropylthiocarbamate(TRIALLATE). Surprisingly, some mixtures also shown a synergisticaction.

A mixture with other known active compounds, such as fungicides,insecticides, acaricides, nematicides, bird repellents, plant nutrientsand agents which improve soil structure, is also possible.

The active compounds can be used as such, in the form of theirformulations or in the use forms prepared therefrom by further dilution,such as ready-to-use solutions, suspensions, emulsions, powders, pastesand granules. They are used in the customary manner, for example bywatering, spraying, atomizing or scattering.

The active compounds according to the invention can be applied eitherbefore or after emergence of the plants.

They can also be incorporated into the soil before sowing.

The amount of active compound used can vary within a substantial range.It depends essentially on the nature of the desired effect. In general,the amounts used are between 0.01 and 10 kg of active compound perhectare of soil surface, preferably between 0.05 and 5 kg per ha.

The preparation and use of the active compounds according to theinvention can be seen from the following examples.

PREPARATION EXAMPLES EXAMPLE 1 ##STR80##

2.52 g (0.02 mol) of 5-methyl-isoxazole-3-carboxamide are dissolved in50 ml of 1,4-dioxane and after adding 3.4 g (0.06 mol) of powderedpotassium hydroxide the mixture is stirred at 80° C. for 30 minutes. Themixture is cooled, 5.7 g (0.022 mol) of methyl 2-chlorosulphonylbenzoateare added at room temperature for 20 hours. The solvent is thendistilled off in vacuo, the residue is taken up in water and thesolution is filtered. The product precipitates from the filtrate onacidifying with hydrochloric acid, and is collected on a suction filterand dried on clay.

1.8 g (27% of theory) ofN-(2-methoxycarbonylphenylsulphonyl)-5-methyl-isoxazole-3-carboxamide ofmelting point 101° C. are obtained.

EXAMPLE 2 ##STR81##

3.8 g (0.02 mol) of 2-chlorobenzenesulphonamide are converted into thesodium salt by dissolving it in 100 ml of methanol, adding 1.1 g (0.02mol) of sodium methoxide, subsequently stirring for 10 minutes andevaporating to dryness. The sodium salt is heated under reflux in 100 mlof acetonitrile with 3.4 g (0.02 mol) of ethyl3-ethyl-1,2,4-oxadiazole-5-carboxylate for 12 hours. The residueremaining after distilling off the solvent is stirred with 100 ml of 10%strength potassium carbonate solution, filtered off with suction, washedwith 1N hydrochloric acid and water and dried in a desiccator.

4.6 g (73% of theory) ofN-(2-(chlorophenylsulphonyl)-3-ethyl-1,2,4-oxadiazole-5-carboxamide ofmelting point 142° C. are obtained.

The compounds of the formula (I) shown in Table 2 below can also beprepared, for example, analogously to Examples 1 or 2 and correspondingto the general description of the preparation process according to theinvention.

    R.sup.1 --CO--NH--SO.sub.2 --(A).sub.n --R.sup.2           (I)

                                      TABLE 2    __________________________________________________________________________    Examples of the compounds of the formula (I)                                   Melting    Ex. No.         R.sup.1     A  n  R.sup.2 point (°C.)    __________________________________________________________________________          ##STR82##  -- 0                            ##STR83##                                   110    4          ##STR84##  -- 0                            ##STR85##    5          ##STR86##  -- 0                            ##STR87##    6          ##STR88##  -- 0                            ##STR89##                                   185    7          ##STR90##  -- 0                            ##STR91##                                   167    8          ##STR92##  -- 0                            ##STR93##                                   145    9          ##STR94##  -- 0                            ##STR95##    10          ##STR96##  CH.sub.2                        1                            ##STR97##                                   120    11          ##STR98##  CH.sub.2                        1                            ##STR99##                                   115    12          ##STR100## -- 0                            ##STR101##    13          ##STR102## -- 0                            ##STR103##    14          ##STR104## -- 0                            ##STR105##                                   112    15          ##STR106## -- 0                            ##STR107##                                   107    16          ##STR108## -- 0                            ##STR109##                                    80    17          ##STR110## -- 0                            ##STR111##                                   196    18          ##STR112## -- 0                            ##STR113##                                   148    19          ##STR114## -- 0                            ##STR115##                                   175    20          ##STR116## -- 0                            ##STR117##                                   197    21          ##STR118## -- 0                            ##STR119##                                   147    22          ##STR120## -- 0                            ##STR121##    23          ##STR122## -- 0                            ##STR123##    24          ##STR124## -- 0                            ##STR125##                                   147    25          ##STR126## -- 0                            ##STR127##                                   147    26          ##STR128## -- 0                            ##STR129##                                   197    27          ##STR130## CH.sub.2                        1                            ##STR131##                                   118    __________________________________________________________________________

EXAMPLE 28

The sodium salt of the compound shown as Example 9 can be prepared, forexample, as follows: ##STR132##

3.0 g (9.5 mmol) ofN-(2-chloro-6-methyl-phenylsulphonyl)-5-methyl-isoxazole-3-carboxamideare dissolved in 50 ml of methylene chloride; 0.4 g (9.5 mmol) of sodiumhydroxide (powder) is then added to this solution and the mixture isstirred at 20° C. for 12 hours. The product which is obtained incrystalline form is isolated by filtering off with suction.

2.5 g (77% of theory) of sodiumN-(2-chloro-6-methylphenylsulphonyl)-5-methyl-isoxazole-3-carboxamide ofmelting point 270° C. (decomposition) are obtained.

Examples of other salts which can be obtained analogously are shownbelow.

EXAMPLE 29 ##STR133## EXAMPLE 30 ##STR134##

Other compounds of the formula (I) which can be prepared analogously toExamples 1 and 2 are: ##STR135##

USE EXAMPLES EXAMPLE A Pre-emergence test

Solvent: 5 parts by weight of acetone.

Emulsifier: 1 part by weight of alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

Seeds of the test plants are sown in normal soil and, after 24 hours,watered with the preparation of the active compound. It is expedient tokeep constant the amount of water per unit area. The concentration ofthe active compound in the preparation is of no importance, only theamount of active compound applied per unit area being decisive. Afterthree weeks, the degree of damage to the plants is rated in % damage incomparison to the development of the untreated control. The figuresdenote:

0%=no action (like untreated control)

100%=total destruction

In this test, the compound according to Preparation Example 1 exhibits avery good herbicidal activity combined with good tolerability by theproductive plants.

EXAMPLE B Post-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

Test plants which have a height of 5-15 cm are sprayed with thepreparation of the active compound in such a way as to apply theparticular amounts of active compound desired per unit area. Theconcentration of the spray liquor is so chosen that the particularamounts of active compound desired are applied in 1,000 l of water/ha.After three weeks, the degree of damage to the plants is rated in %damage in comparison to the development of the untreated control. Thefigures denote:

0%=no action (like untreated control)

100%=total destruction

In this test, the compound according to Preparation Example 1 exhibits avery good herbicidal action combined with excellent cultivated plantselectivity.

It will be understood that the specification and examples areillustrative but not limitative of the present invention and that otherembodiments within the spirit and scope of the invention will suggestthemselves to those skilled in the art.

We claim:
 1. A sulphonylated carboxamide of the formula

    R.sup.1 --CO--NH--SO.sub.2 --(A).sub.n --R.sup.2           (I)

in which n represents the number 0 or 1, A represents oxygen, imino (NH)or methylene (CH₂), R¹ represents a five-membered heretoaryl radicalfrom the group consisting of oxazolyl, isoxazolyl, thiazolyl,isothiazolyl, oxadiazolyl and thiadiazolyl, which is optionallymonosubstituted or polysubstitututed by identical or different halogenor by optionally halogen-substituted C₁ -C₆ -alkyl, phenyl, C₁ -C₆-alkoxy, C₁ -C₆ -alkylthio, C₁ -C₆ -alkylsulphinyl, C₁ -C₆-alkylsulphonyl, C₁ -C₆ -alkylamino or di-(C₁ -C₆ -alkyl)amino, and R²represents the radical ##STR136## in which R³ and R⁴ are identical ordifferent and represent hydrogen, fluorine, chlorine, bromine, iodine,cyano, nitro, carboxyl or C₁ -C₆ -alkyl which is optionally substitutedby fluorine, chlorine, bromine, cyano, carboxyl, C₁ -C₄ -alkoxycarbonyl,C₁ -C₄ -alkylamino-carbonyl, di-(C₁ -C₄ -alkyl)aminocarbonyl, hydroxyl,C₁ -C₄ -alkoxy, formyloxy, C₁ -C₄ -alkyl-carbonyloxy, C₁ -C₄-alkoxycarbonyloxy, C₁ -C₄ -alkylamino-carbonyloxy, C₁ -C₄ -alkylthio,C₁ -C₄ -alkylsulphinyl, C₁ -C₄ -alkylsulphonyl, di-(C₁ -C₄-alkyl)aminosulphonyl, C₃ -C₆ -cycloalkyl or phenyl, or R³ and R⁴furthermore independently of one another represent C₂ -C₆ -alkenyl whichis optionally substituted by fluorine, chlorine, bromine, cyano, C₁ -C₄-alkoxycarbonyl, carboxyl or phenyl, or R³ and R⁴ additionallyindependently of one another represent C₂ -C₆ -alkinyl which isoptionally substituted by fluorine, chlorine, bromine, cyano, C₁ -C₄-alkoxy-carbonyl, carboxyl or phenyl; C₁ -C₄ -alkoxy which is optionallysubstituted by fluorine, chlorine, bromine, cyano, carboxyl, C₁ -C₄-alkoxyacarbonyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₁ -C₄-alkylsulphinyl or C₁ -C₄ -alkylsulphonyl; C₁ -C₄ -alkylthio which isoptionally substituted by fluorine, chlorine, bromine, cyano, carboxyl,C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl or C₁-C₄ -alkylsulphonyl; C₃ -C₆ -alkenyloxy which is optionally substitutedby fluorine, chlorine, bromine, cyano or C₁ -C₄ -alkoxy-carbonyl, C₂ -C₆-alkenylthio which is optionally substituted by fluorine, chlorine,bromine, cyano, nitro, C₁ -C₃ -alkylthio or C₁ -C₄ -alkoxy-carbonyl; C₃-C₆ -alkynyloxy, C₃ -C₆ -alkylthio or the radical --S(O)_(p) --R⁵, or R³and R⁴ furthermore represent phenyl or phenoxy, C₁ -C₄-alkylcarbonylamino, C₁ -C₄ -alkoxycarbonylamino, C₁ -C₄-alkylamino-carbonylamino, di-(C₁ -C₄ -alkyl)-amino-carbonylamino, orthe radical --CO--R⁶, or R³ and R⁴ furthermore represent C₁ -C₄-alkylsulphonyloxy, di-(C₁ -C₄ -alkyl)-aminosulphonylamino or theradical --CH═N--R⁷, in whichp represents the numbers 1 or 2 and R⁵represents C₁ -C₄ -alkyl which is optionally substituted by fluorine,chlorine, bromine, cyano or C₁ -C₄ -alkoxycarbonyl, or R⁵ represents C₁-C₄ -alkoxy, C₁ -C₄ -alkoxy-C₁ -C₄ -alkylamino or di-(C₁ -C₄-alkyl)-amino, R⁶ represents C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy which isoptionally substituted by fluorine, chlorine, methoxy or ethoxy; C₃ -C₆-cycloalkoxy, C₃ -C₆ -alkenyloxy, C₁ -C₄ -alkylthio, amino, C₁ -C₄-alkylamino, C₁ -C₄ -alkoxyamino, C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl-amino ordi-(C₁ -C₄ -alkyl)amino which are optionally substituted by fluorine orchlorine and R⁷ represents C₁ -C₆ -alkyl which is optionally substitutedby fluorine, chlorine, cyano, carboxyl, C₁ -C₄ -alkoxy, C₁ -C₄-alkylthio, C₁ -C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl, benzylwhich is optionally substituted by fluorine or chlorine, C₃ -C₆ -alkenylor C₃ -C₆ -alkynyl which are optionally substituted by fluorine orchlorine, phenyl which is optionally substituted by fluorine, chlorine,bromine, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, trifluoromethyl,trifluoromethoxy or trifluoromethylthio, C₁ -C₆ -alkoxy, C₃ -C₆-alkenyloxy, C₃ -C₆ -alkynyloxy or benzyloxy which are optionallysubstituted by fluorine or chlorine, or R⁷ furthermore represents amino,C₁ -C₄ -alkylamino, di(C₁ -C₄ -alkyl)-amino, phenylamino, C₁ -C₄-alkyl-carbonylamino, C₁ -C₄ -alkoxycarbonylamino, C₁ -C₄-alkyl-sulphonylamino or phenyl sulphonylamino which is optionallysubstituted by fluorine, chlorine, bromine or methyl, R¹⁰ and R¹¹ areidentical or different and represent hydrogen, fluorine, chlorine,bromine, nitro, cyano, or C₁ -C₄ -alkyl which is optionally substitutedby fluorine or chlorine; C₂ -C₄ -alkenyl which is optionally substitutedby fluorine or chlorine, C₁ -C₄ -alkoxy which is optionally substitutedby fluorine or chlorine; C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl or C₁-C₄ -alkylsulphonyl which are optionally substituted by fluorine orchlorine; and di-(C₁ -C₄ -alkyl)-aminosulphonyl, C₁ -C₄-alkoxy-carbonyl, dimethylaminocarbonyl or dioxolanyl; or a saltthereof, with the exclusion of the compound2-(dimethylamino)-N-[(4-methylphenyl)sulphonyl]-5-thiazole carboxamide.2. A sulphonylated carboxamide according to claim 1, in whichnrepresents the numbers 0 or 1, A represents oxygen, imino (NH) ormethylene (CH₂), R¹ represents a five-membered heteroaryl radical fromthe group consisting of oxazolyl, isoxazolyl, thiazolyl,1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,4-thiadiazolyl and1,3,4-thiadiazolyl, which is optionally substituted by fluorine,chlorine, bromine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl,sec-butyl, tert-butyl, fluoromethyl, chloromethyl, difluoromethyl,dichloromethyl, trifluoromethyl, trichloromethyl, chlorofluoromethyl,chlorodifluoromethyl fluorodichloromethyl, phenyl, methoxy, ethoxy,propoxy, isopropyloxy, difluoromethoxy, trifluoromethoxy,chlorodifluoromethoxy, methylthio, ethylthio, propylthio, isopropylthio,difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio,methylsulphinyl, ethylsulphinyl, propylsulphinyl, methylsulphonyl,ethylsulphonyl, propylsulphonyl, methylamino, ethylamino, propylamino,isopropylamino or dimethylamino, and R² represents the radical##STR137## in which R³ represents hydrogen, fluorine, chlorine, bromine,cyano, nitro, carboxyl, methyl, trifluoromethyl, methoxy, ethoxy,2-chloroethoxy, difluoromethoxy, trifluoromethoxy, C₁ -C₃ -alkylthio, C₁-C₃ -alkyl-sulphinyl, C₁ -C₃ -alkylsulphonyl, dimethylaminosulphonyl,diethylaminosulphonyl, N-methoxy-N-methylaminosulphonyl, phenyl, phenoxyor C₁ -C₃ -alkoxycarbonyl and R⁴ represents hydrogen, fluorine,chlorine, bromine, methyl, trifluoromethyl or methoxy, R¹⁰ representsdimethylaminocarbonyl or C₁ -C₄ -alkylsulphonyl, and R¹¹ representshydrogen, fluorine or chlorine or a salt thereof, with the exclusion ofthe compound 2-(dimethylamino)-N-[(4-methylphenyl)-sulphonyl]-5-thiazolecarboxamide.
 3. A method of combating unwanted vegetation whichcomprises applying to such vegetation or to a locus from which is itdesired to exclude such vegetation a herbicidally effective amount of asulphonylated carboxamide of the formula

    R.sup.1 --CO--NH--SO.sub.2 --(A).sub.n --R.sup.2           (I)

in which n represents the numbers of 0 or 1, A represents oxygen, imino(NH) or methylene (CH₂), R¹ represents a five-membered heteroarylradical from the group consisting of oxazolyl, isoxazolyl, thiazolyl,isothiazolyl, oxadiazolyl and thiadiazolyl, which is optionallymonosubstituted or polysubstituted by identical to different halogen orby optionally halogen-substituted C₁ -C₆ -alkyl, phenyl, C₁ -C₆ -alkoxy,C₁ -C₆ -alkylthio, C₁ -C₆ -alkylsulphinyl, C₁ -C₆ -alkylsulphonyl, C₁-C₆ -alkylamino or di-(C₁ -C₄ -alkyl)amino, and R² represents theradical ##STR138## in which R³ and R⁴ are identical or different andrepresent hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro,carboxyl or C₁ -C₆ -alkyl which is optionally substituted by fluorine,chlorine, bromine, cyano, carboxyl, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄-alkylamino-carbonyl, di-(C₁ -C₄ -alkyl)aminocarbonyl, hydroxyl, C₁ -C₄-alkoxy, formyloxy, C₁ -C₄ -alkyl-carbonyloxy, C₁ -C₄-alkoxycarbonyloxy, C₁ -C₄ -alkylamino-carbonyloxy, C₁ -C₄ -alkylthio,C₁ -C₄ -alkylsulphinyl, C₁ -C₄ -alkylsulphonyl, di-(C₁ -C₄-alkyl)aminosulphonyl, C₃ -C₆ -cycloalkyl or phenyl, or R³ and R⁴furthermore independently of one another represent C₂ -C₆ -alkenyl whichis optionally substituted by fluorine, chlorine, bromine, cyano, C₁ -C₄-alkoxycarbonyl, carboxyl or phenyl, or R³ and R⁴ additionallyindependently of one another represent C₂ -C₆ -alkinyl which isoptionally substituted by fluorine, chlorine, bromine, cyano, C₁ -C₄-alkoxy-carbonyl, carboxyl or phenyl; C₁ -C₄ -alkoxy which is optionallysubstituted by fluorine, chlorine, bromine, cyano, carboxyl, C₁ -C₄-alkoxycarbonyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₁ -C₄-alkylsulphinyl or C₁ -C₄ -alkylsulphonyl; C₁ -C₄ -alkylthio which isoptionally substituted by fluorine, chlorine, bromine, cyano, carboxyl,C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl or C₁-C₄ -alkylsulphonyl; C₃ -C₆ -alkenyloxy which is optionally substitutedby fluorine, chlorine, bromine, cyano or C₁ -C₄ -alkoxy-carbonyl, C₂ -C₆-alkenylthio which is optionally substituted by fluorine, chlorine,bromine, cyano, nitro, C₁ -C₃ -alkylthio or C₁ -C₄ -alkoxy-carbonyl; C₃-C₆ -alkynyloxy, C₃ -C₆ -alkynylthio or the radical --S(O)_(p) --R⁵, orR³ and R⁴ furthermore represent phenyl or phenoxy, C₁ -C₄-alkylcarbonylamino, C₁ -C₄ -alkoxycarbonylamino, C₁ -C₄-alkylamino-carbonylamino, di-(C₁ -C₄ -alkyl)-amino-carbonylamino, orthe radical --CO--R⁶, or R³ and R⁴ furthermore represent C₁ -C₄-alkylsulphonyloxy, di-(C₁ -C₄ -alkyl)-aminosulphonylamino or theradical --CH═N--R⁷, in whichp represents the numbers 1 or 2and R⁵represents C₁ -C₄ -alkyl which is optionally substituted by fluorine,chlorine, bromine, cyano or C₁ -C₄ -alkoxycarbonyl, or R⁵ represents C₁-C₄ -alkoxy, C₁ -C₄ -alkoxy-C₁ -C₄ -alkylamino or di(C₁ -C₄-alkyl)-amino, R⁶ represents C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy which isoptionally substituted by fluorine, chlorine, methoxy or ethoxy; C₃ -C₆-cycloalkoxy, C₃ -C₆ -alkenyloxy, C₁ -C₄ -alkylthio, amino, C₁ -C₄-alkylamino, C₁ -C₄ -alkoxyamino, C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl-amino ordi-(C₁ -C₄ -alkyl)amino which are optionally substituted by fluorine orchlorine and R⁷ represents C₁ -C₆ -alkyl which is optionally substitutedby fluorine, chlorine, cyano, carboxyl, C₁ -C₄ -alkoxy, C₁ -C₄-alkylthio, C₁ -C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl, benzylwhich is optionally substituted by fluorine or chlorine, C₃ -C₆ -alkenylor C₃ -C₆ -alkynyl which are optionally substituted by fluorine orchlorine, phenyl which is optionally substituted by fluorine, chlorine,bromine, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, trifluoromethylthio, C₁ -C₆-alkoxy, C₃ -C₆ -alkenyloxy, C₃ -C₆ -alkynyloxy or benzyloxy which areoptionally substituted by fluorine or chlorine, or R⁷ furthermorerepresents amino, C₁ -C₄ -alkylamino, di(C₁ -C₄ -alkyl)-amino,phenylamino, C₁ -C₄ -alkyl-carbonylamino, C₁ -C₄ -alkoxycarbonylamino,C₁ -C₄ -alkyl-sulphonylamino or phenyl sulphonylamino which isoptionally substituted by fluorine, chlorine, bromine or methyl, R¹⁰ andR¹¹ are identical or different and represent hydrogen, fluorine,chlorine, bromine, nitro, cyano, or C₁ -C₄ -alkyl which is optionallysubstituted by fluorine or chlorine; C₂ -C₄ -alkenyl which is optionallysubstituted by fluorine or chlorine, C₁ -C₄ -alkoxy which is optionallysubstituted by fluorine or chlorine; C₁ -C₄ -alkylthio, C₁ -C₄-alkylsulphinyl or C₁ -C₄ -alkylsulphonyl which are optionallysubstituted by fluorine or chlorine; and di-(C₁ -C₄-alkyl)-aminosulphonyl, C₁ -C₄ -alkoxy-carbonyl, dimethylaminocarbonylor dioxolanyl; or a salt thereof.
 4. A salt of a compound according toclaim 1, with the hydroxide, hydride, amide or carbonate or sodiumpotassium or calcium, the C₁ -C₄ -alkoxide of sodium or potassium,ammonia, an C₁ -C₄ -alkylamine, di-(C₁ -C₄ -alkyl)-amine or tri-(C₁ -C₄-alkyl)-amine.
 5. A sulphonylated carboxamide according to claim 1, inwhichR² represents the radical ##STR139##
 6. A sulphonylated carboxamideaccording to claim 5, in which R⁴ is hydrogen.
 7. A compound accordingto claim 1, wherein such compound isN-(2-methoxycarbonyl-phenylsulphonyl)-5-methyl-isoxazole-3-carboxamideof the formula ##STR140## or a salt thereof.
 8. A herbicidal compositioncomprising a herbicidally effective amount of a compound of saltaccording to claim 1 and a diluent.
 9. A method of combating unwantedvegetation which comprises applying to such vegetation or to a locusfrom which it is desired to exclude such vegetation a herbicidallyeffective amount of a compound or salt according to claim
 7. 10. Asulphonylated carboxamide of the formula ##STR141## in which nrepresents the numbers 0 or 1,A represents oxygen, imino (NH) ormethylene (CH₂), R¹ represents a five-membered heteroaryl radical fromthe group consisting of oxazolyl, isoxazolyl, thiazolyl, isothiazolyl,oxadiazolyl and thiadiazolyl, which is optionally monosubstituted orpolysubstituted by identical or different halogen or by optionallyhalogen-substituted C₁ -C₆ -alkyl, phenyl, C₁ -C₆ -alkoxy, C₁ -C₆-alkylthio, C₁ -C₆ -alkylsulphinyl, C₁ -C₆ -alkylsulphonyl, C₁ -C₆-alkylamino or di-(C₁ -C₄ -alkyl)-amino, and R² represents fluorine,chlorine, bromine, iodine, cyano, nitro, carboxyl, C₁ -C₄ -alkyl, C₁ -C₄-alkoxy, C₁ -C₄ -alkylthio, phenyl, C₁ -C₄ -alkylsulphinyl, C₁ -C₄-alkylsulphonyl, di-(C₁ -C₄ -alkyl)-aminosulphonyl, or the radical--S(O)_(p) --R⁵, p represents the numbers 1 or 2 and R⁵ represents C₁-C₄ -alkoxy-C₁ -C₄ -alkylamino which are optionally substituted byfluorine or chlorine, furthermore represents C₁ -C₄ -alkoxycarbonyl,which is optionally substituted by fluorine, chlorine, or C₁ -C₄-alkoxy, R³ represents hydrogen, fluorine, chlorine, bromine, methyl, ora salt thereof, with the exclusion of the compound2-(dimethylamino)-N-[(4-methylphenyl) sulphonyl]-5-thiazole carboxamide.11. A compound according to claim 1, wherein such compound isN-(2-methoxycarbonyl-phenylsulphonyl)-3-methyl-1,2,4-oxadiazole-5-carboxamideof the formula ##STR142##